Process of impregnating fibrous materials and the material thus obtained



Patented Mar. 11, 1941 OFFICE PROCESS OF WREGNATIN G FIBROUS MATERIALS AND THE MATERIAL THUS OBTAINED Joseph Niisslein and Georg yon Finck, Frankiort-on-the-Main, Germany, assignors to I. G. Farbenindustrie Aktiengesellschait, Frankfort-on-the-Maln, Germany No Drawing. Application January 8, 1938,

Serial No. 184,106. 1937 8 Claims. The present invention relates to a process of impregnating fibrous materials'and to the material thus obtained; more particularly, it relates to water-proofing fibrous materials, especially textile materials.

In U. S. patent application Serial No. 184,104 filed Jan. 8, 1938, in the name of Arnold Brunner and Georg von Finck, for: Process of impregnating fibrous material and the material thus obtained there is described a process of water-proofing artificial or natural materials, such as fibers, yarns, ribbons, threads, textile fabrics and similar materials by impregnating them with solutions or emulsions of substances obtainable according to the process of application Serial No. 168,681, filed October 12, 1937, now U. S. Patent No. 2,180,791 dated Nov. 21, 1939, a division of application Serial N0. 128,025

filed February 26, 1937, now U. S. Patent No.

2,165,956, dated July 11, 1939, in the name of Arnold Brunner, for: Condensation products and a process of preparing them. There may be used materials from cellulose fibers, such as cotton, viscose artificial silk, cuprammonium artificial silk, materials from cellulose esters or cellulose ethers, further products from animal fibers, such as wool and silk, or mixed fabrics of the above-mentioned materials, for instance, half-wool or mixtures of wool and artificial silk staple fiber. There may also be. impregnated other fibers found in nature, such as hemp, flax, jute, ramie.

The products used for the impregnation are prepared in the following manner: Phenols containing in the nucleus one or more long aliphatic chains are treated with aqueous formaldehyde solutions and hydrogen chloride. The chloromethyl derivatives of the phenols thus obtained having the formula A.CH:.CI, wherein A represents a-radical of a phenol substituted by an aliphatic hydrocarbon radical having at least 4 carbon atoms are caused to react with organic nitrogen bases, especially tertiary amines, such as pyridine, triethylamine or the like. In the latter case the corresponding quaternary ammonium compounds are formed. The textiles treated with the above-mentioned products retain the property of being water-proof even after they have been washed and cleaned, for instance, with soap and sodium carbonate.

We have found that the fibrous materials may be made even much more water-repellent by using the said compounds in combination with mixed polymerisates from unsaturated carboxylic acids or the derivatives thereof and ole- In Germany August 3,

finic compounds wherein at leastone of the components composing the mixed polymerisate contains an aliphatic radical with at least 10 carbon atoms in one chain. I a There may be used, for' instance, the following products: the mixed polymerizate (also called interpolymer) from maleic anhydride and vinyl-octodecyl ether; the mixed polymerizate from maleic acid monomethyl ester and stearic acid vinyl ester; the free acid of the mixed polymeriz'ate from maleic anhydride and a vinyl ether or a vinyl ester, for instance vinyl-octodecyl ether; the mixed polymerizate from maleic acid mono-dodecyl ester and vinyldodecyl ether. Furthermore, there may be used maleic anhydride in combination with vinyl stearate or vinyl palmitate. Instead of the abovementioned vinyl-octodecyl ether, there may be used the vinyl ether of the alcohol mixture formed by the reduction of coconut. oil fatty acids and containing, for the main part, compounds with 12 to 14 carbon atoms, or the vinyl ether of the montan-wax alcohol. Another mixed polymerizate suitable for use may be obtained from maleic anhydride and isohexadecylene. Instead of the maleic anhydride there may also be used for the common polymerization the monoor di-esters derived from maleic acid and aliphatic alcohols. These aliphatic alcohols may be of low or of high molecular weight. If the maleic acid ester contains a radical of high molecular weight, it is not always necessary that the vinyl compound used for preparing the mixed polymerizate should be of high molecular weight. Thus, there may be used as mixed polymerizates in some cases compounds such as vinyl acetate, vinyl chloride etc. together with maleic acid esters of high molecular weight. Furthermore, maleic acid dihexyadecyl ester, for instance, may be used in combination with methacrylic acid methyl ester, vinyl-ethyl ether or vinyl-methyl ether. There may also be used other derivatives of maleic acid, such as the nitrile or the acid By the joint application of both groups or chemical compounds hydrophobic impregnations are obtained which do not lose their hydrophobic properties even after they have been washed one or several times with soap, soap in combination with sodium carbonate or benzine. The degree of the hydrophobic effect is essentially higher than that obtained on textile materials which have been treated with the mixed polymerizates or with the products obtained from chloromethyl compounds of phenols and organic nitrogen bases, even when used in larger proportion.

The goods may be imregnated with the said compounds simultaneously in one bath or in any order in different baths; there may be used solutions or emulsions. Solvents suitable for the mixed polymerizates are, for instance, hydrocarbons and chlorinated hydrocarbons, such as benzine, benzene, carbon tetrachloride, trichlorethylene and mixtures of these solvents with methanol or ethanol. The inter-polymers may also be brought into an aqueous emulsion, preferably while adding an emulsifying agent, and the material may be impregnated with this emulsion. It is, furthermore, possible to dissolve the interpolymers in paraflin or in paramn oil and to emulsify this solution in water. For the compounds formed by reacting the chloromethyl compound of phenols with organic ni-- trcgen bases there may, for instance, be used the following solvents: water, methanol, ethanol, mixtures of these alcohols with benzine and carbon tetrachloride.

After impregnating in one or several baths,

vthe material is squeezed or centrifuged, dried pounds spiltting off acids or having an acid reaction may be added to the impregnating liquids. The reaction may, however, also take place in the absence of acid substances. By the impregnation with aldehydes, or aldehyde resins and subsequent heating, fastness to creasing and a further increase of the hydrophobic properties are obtained. a

' The following examples serve to illustrate the invention, but they are not intended to limit it thereto; the parts are by weight:

1) 10 parts of the interpolymer from maleic anhydride and vinyl octodecyl ether are melted together with parts of parafiin (melting at 52 C.) and the melt is stirred into a solution of '7 parts of polyvinyl alcohol or of the sodium salt of polyacrylic acid in 100 parts of water and the emulsion thus obtained is homogenized in a suitable apparatus. dispersed emulsion are diluted with 1000 cc. of water. Loose artificial silk staple fiber is impregnated with this liquor, then squeezed, or centrifuged, and dried subsequently. Thereupon the material is once more impregnated in a second bath containing per liter of water 10 grams of the pyridinium compound from chloromethyl-isododecylphenol and dried at C.- C.

50 grams of the finely (2) Artificial silk crepe is treated for 5 minutes in a solution containing per liter of carbon tetrachloride 5 grams of the interpolymer from maleic anhydride and. vinyldodecyl ether, squeezed, and subsequently impregnated once more in a second bath containing per liter of water 10 grams of the pyridinium compound from chloromethyl-isooctylphenol, and dried at 120 C.

(3) A fabric made from artificial silk or cotton is impregnated in a mixture of equal parts of carbon tetrachloride and ethanol containing per liter 5 grams of the free acid of the interpolymer from maleic anhydride and vinyltetradecyl ether, and, furthermore, 5 grams of the trimethylammonium compound from chloromethyl-ndodecylphenol, then squeezed or centrifuged and, after evaporation of the solvents, heated for 15 minutes at C.

(4) Dress-material from wool, natural silk or artificial silk is treated in a solution containing per liter of water 10 grams of the pyridine salt of the free acid of the interpolymer from maleic anhydride and vinyl-stearic acid ester, and, after evaporation of the solvent, heated for 15 minutes at 110 C., subsequently impregnated in a second bath containing per liter of'water 15 grams of the pyridinium compound from chloromethylisobutylphenol, squeezed, or centrifuged, and dried at 100 C.-110 C.

(5) A fabric from artificial silk or cotton is treated for a short time in a solution containing per liter of carbon tetrachloride E grams of the interpolymer from maleic anhydride and vinyl-octodecyl ether and squeezed; after evaporation of the solvent, the fabric is impregnated once more in a second bath containing per liter of water 10 grams of the pyridinium compound from chloromethyl isododecylphenol, 100 grams of dimethylolurea and 3 grams of tartaric acid and subsequently dried at 125 C.

for half an hour.

(6) Mixed fabric from wool and artificial silk or cotton is treated for one minute in a solutiontriethylamine and chloromethyl-isobutylphenol,

squeezed and heated for 1 hour at 110 C.

('7) Dress material from wool, cotton and artificial silk is impregnated in three passages on the foulard with asolution containing per liter of benzine 5 grams of the mixed polymerizate from maleic acid dimethylester and lauric and vinylester, squeezed, dried in the air' and subsequently treated for 5 minutes in a second bath containing per liter of water 10 grams of a condensation product from pyridine and chloromethyl-di-octylphenol, squeezed, dried and heated for 20 minutes at C. (8) A fabric from viscose artificial silk or fabric from 70% of wool and 30% of artificial silk is impregnated with a solution containing per liter of carbon tetrachloride 5 grams of a mixed polymerlzate from vinyl-octadecylether and maleic anhydride, dried in the air and impregnated again in a second bath containing per liter of water 10 grams of a condensation product from pyridine and the technical mixture of the chloromethyl compound from isododecyl, isotridecyl and isotetradecylphenol, squeezed, dried and heated for 30 minutes at 110 C.

We claim:

1. The process which comprises impregnating fibrous materials with organic nitrogen compounds obtainable by causing phenols of the general formula: ACE-2.01, wherein A represents a radical of a phenol substituted by an aliphatic hydrocarbon radical having at least 4 carbon atoms, to react with a nitrogen base selected from the group consisting of tertiary aliphatic and tertiary heterocyclic amines, and with a mixed polymerisate prepared from a compound of the group consisting of maleic anhydride and maleic esters, and from an olefinic compound of the group consisting of vinyl ethers and vinyl esters, the mixed polymerisate containing an aliphatic radical with at least 10 carbon atoms in one chain.

2. The process which comprises impregnating fibrous materials with organic nitrogen compounds obtainable by causing phenols of the general formula: A.CH2.C1, wherein A represents a radical of a. phenol substituted by an aliphatic hydrocarbon radical having at least 4 carbon atoms, to react with a nitrogen base selected from the group consisting of tertiary aliphatic and tertiary heterocyclic amines, and with the free acid of the mixed polymerisate prepared from maleic anhydride and an oleflnic compound of the group consisting of vinyl ethers and vinyl esters, the mixed polymerisate containing an allphatic radical with at least 10 carbon atoms in one chain.

3. The process of waterproofing textile materials which comprises impregnating the said materials with the compound obtainable by condensation of pyridine and the chloromethyl compound of the commercial mixture of iso-dodecyl, iso-tridecyl and iso-tetradecylphenol, and with the mixed polymerisate prepared from maleic anhydride and vinyloctodecyl ether.

4. Theprocess of waterproofing textile materials which comprises impregnating the said materials with the compound obtainable by condensation of pyridine and the chloromethyl compound of iso-dodecylphenol, and with the mixed polymerisate prepared from maleic anhydride and vinyloctodecyl ether in the presence of par- 5. Waterproof fibrous material which has been impregnated with organic nitrogen compounds obtainable by causing phenols of the general formula: A.CH2.C1, wherein A represents a radical of a phenol substituted by an aliphatic hydrocarbon radical having at least 4 carbon atoms, to react with a. nitrogen base selected from the .group consisting of tertiary aliphatic and terradical having at least 4 carbon atoms, to reactwith a nitrogen base selected from the group consisting of tertiary aliphatic and tertiary heterocylic amines, and with the free acid of the mixed polymerisate prepared from maleic anhydride and an olefine compound of the group consisting of vinyl ethers and vinyl esters, the mixed polymerisate containing an aliphatic radical with at least 10 carbon atoms in one chain.

'7, Waterproof textile material which has been impregnated with the compound obtainable by condensation of pyridine and the chloromethyl compound of the commercial mixture of isododecyl, iso-tridecyl and iso-tetradecylphenol, and with the mixed polymerisate prepared from maleic anhydride and vinyl-octodecyl ether.

8. Waterproof textile material which has been impregnated with the compound obtainable by condenesation of pyridine and the chlororomethyl compound of iso-dodecylphenol and with the mixed polymerisate prepared from maleic anhydride and vinyl-octodecyl ether in the presence of parafiine.

JOSEPH NiissLEm. (mom von' FINCK. 

